1,1‐Dihydroperoxides

Abstract

Gem ‐dihydroperoxides ( g ‐DHPs), often referred to as 1,1‐dihydroperoxides, are a class of molecules of interest because of their reactivity as well as their utility as synthetic reagents and intermediates. This review begins with a listing of previous reviews and commercially available g ‐DHPs, followed by a brief discussion of safety and regulatory issues. The properties of g ‐DHPs are then overviewed, with an emphasis on the physical properties, biological activity, thermal stability, spectroscopic properties, and behavior on chromatographic media. The remaining sections describe the synthesis and reactions of g ‐DHPS. The largest of these sections describes the various methods for synthesis of g ‐DHPs based upon class of catalyst or reagent and compares applications of different reagents selected target skeletons. One of the most significant applications of g ‐DHPs, their use as precursors for 1,2,4,5‐tetraoxanes, is discussed in detail, including tabular comparisons of approaches to selected skeletons. The chapter concludes with a discussion of other important reactions of g ‐DHPs, including alkylations, nucleophilic and electrophile‐promoted additions to alkenes, acetalizations, acylations and acylation‐promoted fragmentations, acid‐promoted dimerizations and decompositions, silylations, and application as oxygen transfer agents.

Stereoelectronic Interactions as a Probe for the Existence of the Intramolecular α-Effect

“…This lower stabilization in peroxide-bearing cation should shape the potential energy surface for the equilibrium between the cationic species involved in the acid catalyzed formations of endo- and exocyclic peroxides and hydroperoxides from carbonyl compounds and H 2 O 2 . These processes open synthetic access to a surprising diversity of oxygen-containing functionalities including geminal bis-hydroperoxides, geminal bis-peroxides, tetraoxanes, cyclic triperoxides, tricyclic monoperoxides, and ozonides …”

Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide

“…This approach to the preparation of peroxides benefits from the broad availability of such starting materials and from the great reactivity of nucleophilic peroxide oxygen toward carbonyl compounds. These reactions opened synthetic access to many important classes of peroxides, such as geminal bis-hydroperoxides, geminal bis-peroxides, tetraoxanes, cyclic triperoxides, and tricyclic monoperoxides . However, peroxides containing the 1,2,4-trioxolane moiety (i.e., secondary ozonides) have been traditionally obtained using ozone.…”

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF3-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

“…Currently, the reaction of ketones or aldehydes with H 2 O 2 and hydroperoxides serves as one of the main synthetic approaches to organic peroxides. − Although many publications describe reactions of hydrogen peroxide and monoketones, − the problem of peroxidation selectivity in the presence of several reactive centers has not found a general solution. For β-dicarbonyl compounds, this issue has been successfully addressed only in a small number of literature reports. − It was shown that β-diketones can be transformed into 1,2,4,5-tetraoxanes, , whereas δ-diketones can be converted into 1,2,4-trioxolanes (ozonides) (Scheme ).…”